312 112

(Aldehydes and Ketones)

:
e-mail : chapha@kku.ac.th

1) Vollhardt, K. P. C.; Schore, N. E. Organic Chemistry,

3rd ed. W. H. Freeman Co., New York, 1998.
2) McMurry, J. Organic Chemistry, 3rd ed. Brooks/Cole
Publishing Co., California, 1992.

1)

2)

3)

4)

1)
(carbonyl group)

+ C O


C=O

 (RCHO)

(RCOR)

CH3
O

O
H
H3C

Cinnamaldehyde

CH2

Carvone

CH3
CHO

H
HO
OCH3

Vanillin

H3C

CH3

Citral

H3C

CH3

CH3

CH3

Muscone

Camphor

H3C
CH3

OH

CH3
CH3

CH3

Testosterone

Progesterone

(oC)

56

-7.0 C

0.04 g/100

58

56.5 C

infinite

CH3CH2CH2CH=CH2

70

30.0 C

0.03 g/100

CH3CH2CH2CH=O

72

76.0 C

7 g/100

96

103.0 C

insoluble

98

155.6 C

5 g/100

(CH3)2C=CH2
(CH3)2C=O

CH2

2)
2.1) ( IUPAC)
al

1
O
H

O
H

Methanal

( HCHO )

CH3

Ethanal

OH

1 H

Butanal

O
H

4-Hydroxybutanal

CH3

CH3 CH2 CH CH2 C H

CH3
H3C CH CH2

O
CH CH
CH2CH3

2.2) ()

aldehyde

1 C: formic acid, formaldehyde

2 Cs: acetic acid, acetaldehyde
3 Cs: propionic acid, propionaldehyde
4 Cs: butyric acid, butyraldehyde.
(

O
O

O
OH
OH

Formic acid

Acetic acid

O
H

OH

H3C

O
H

Formaldehyde

H3C

Br

Acetaldehyde

Br

 CHO
carbaldehyde
CHO

CHO

2-cyclopentenecarbaldehyde

2.3) ( IUPAC)

-one


O
H3C

O
CH3

Propanone

CH3

C CH CH3
CH3

3-methyl-2-butanone

O
CH3

C CH CH2OH
CH3

4-hydroxy-3-methyl-2-butanone
H3C

CH2 CH2 C

CH3

O
C

CH2

CH3

 (cyclic ketones)
1
O

O
1
4

2
3

Br

3-bromocyclohexanone
O

O
CH3

H3C
H3C

CH3

Br
CH3

2.4) ()
ketone

O

H3C

H3C

CH3

Dimethyl ketone

Ethyl methyl ketone

O
CH3

CH2CH3

CH3CH C CH CH3

C CH CH3
CH3

methyl isopropyl ketone

Br

CH3

-bromoethyl isopropyl ketone

 IUPAC
O
CH3

C CH3

CH3

acetone
benzophenone

acetophenone

CH3

HO

CH3

CH CH2

C H

CH3

COOH

CH3

CH3

CH CH2

C H

3-methyl-4-oxopentanal

CHO

3-formylbenzoic acid

O
HC

CCH

Propynal

(6S)-chloro-3-hepten-2-one
O

O
H

3-cyclobutyl-3-oxopropanal

 1.
O

O
O

OH
H

O
H

A. (E)-4-Methyl-4-hexenal

B. 2-Hydroxybutanal

C. 3-Hydroxybutanal

D. 4-Octyn-3-one

E. 4-Octyn-6-one

F. 2-Cyclohexenone

 2.

3-Hexaone

3-Methyl-3-butenal

4-Hexen-2-one

4-Chloro-2-pentanone

2,4-Hexanedione

Butanedial

3-Methylbutanal

4-Methyl-3-penten-2-one

Phenylacetaldehyde

3-Phenyl-2-propenal

3)
1. 1o 2o

2. Friedel-Crafts acylation
Acid chloride/AlCl3 + benzene
ketone
+

3. (Hydration) terminal alkyne

HgSO4, H2SO4, H2O methyl
ketone
Sia2BH H2O2 NaOH
aldehyde

4. (Ozonolysis) alkene
R'

H
C
R

C
R''

1) O3
2) (CH3)2S

CH3

R'

H
C O

+ O C

1). O3
2). Me2S

R''

5. (Acylchlorides)
Cl

LiAlH(O Bu)3

O2N

O2N

Cl

CH3

2 O2N

+ (CH3)2CuLi
O

2 O2N
O


Acidic Proton

H
C
R

C
C

Electrophile

()

Nucleophile

()

4.1) ,
4.2)

4.3) - (-Carbon)

4.1) ,
4.1.1) (
)

4.1.2) (hydride)

4.2)

HO

(hydroxide ion)

HOH (water)

(hydride ion)

ROH (alcohol)

R3C (carbanion)
RO

(alkoxide ion)

NC

(cyanide ion)

H3N (ammonia)
RNH2 (amine)

 (Hydration)

O
H

HO
+ H2O
H

OH
C
H

(OH-)

1o carbocation

R'

2o carbocation

O -

O -

C +

C +
H

Aldehyde

R'
Ketone

(Steric Hindrance)

 Keq

 Keq

 (Acetal Formation)



(H+)
(, ROH)
(hemiacetal)

(acetal)
(reversible)

 (hemiacetal)
O

+ OH

H+

OH
+

OH

HO
HOCH3

HO
OCH3
+
HOCH3

OCH3
+
+ H2OCH3

(acetal)
(hemiacetal)
HO

OCH3

+
HO

H
OCH3

OCH3
+

H+

+ HOH

HOCH3
OCH3
HOCH3

+
CH3O

H
OCH3

CH3O

OCH3

Cyclic Acetals
(diols)

CH2 CH2
O
O

O
+

CH2
HO

CH2
OH


H+
-H2O

H+
-H2O

 hemiacetals
acetals

 (Cyanohydrin Formation)
O
CH3CH2

HO
CH3

+ HCN

CH3CH2

CN
C
CH3

KCN(aq)
C O

CN -

room
temperature

H+

H+(aq)

C
H

OH
C

CN

CN

HCN
NaCN KCN

formaldehyde > aldehydes >
ketones >> ketones


(Primary Amines)/ (NH3)

C=O C=N-R
CH3

H3C
RNH2

C O
Ph

CH3

N C OH
H
Ph

R
_
C
H2N
O
+ Ph

CH3

N C OH
H
Ph

CH3
N C
Ph

(, Imine)

 (Imines)


(Secondary Amines) (enamines)

 (Enamines)

 3.
1.
2.
3.
4.
5.
6.

A.

E.

acetal
oxime
enamine
cyanohydrin
Cyclic hemiacetal
(Intermediate) imime

B.

C.
F.

D.
G.

H.

 Organometallic Reagents
(Alcohol Formation)

/Grignard Reagent
organic halides

 /Grignard Reagent
1
2

 4.


(Deoxygenation)
C=O CH2
:
Clemmensen

Wolff-Kishner

 Clemmensen
O
C

CH2CH3

Zn(Hg)

CH2CH2CH3

HCl, H2O

O
CH2

Zn(Hg)
H

HCl, H2O

CH2

CH3

 Clemmensen

 Wolff-Kishner
CH2

C H

H2N NH2

CH2

C H
NNH2

KOH
heat

CH2

CH3

 Wittig (The Wittig Reaction)

phosphorus ylides
C=O C=C

 Wittig
ylides betaine
phosphine phosphine
oxide
+
+
Ph3P

Ph3P

H3C
C O

CHCH3
Ph

+
Ph3P

_
O

C CH3
CH3 Ph

H C

Ph3P

C CH3
CH3 Ph

C CH3
CH3 Ph

H C

Ph3P
H

H C

H3C

O
C

CH3
Ph

 Wittig

4.3) - (-Carbon)

KetoEnol Tautomerism

 tautomerism

 tautomerism

 The Aldol Reaction


(-Elimination)

 Iodoform Test
-methyl
NaOI
NaOH

I2

NaOI

HI

(Sodium
Hypoiodite)
H
R

C
OH

CH3 + NaOI

C
O

CH3 + NaI + H2O

 5.
1-Phenylethanol Benzene Ethanol

?
MgBr

CH3CH2OH

H
C

O
H3C

OH
H

CH3

 6.